Method for the preparation of 1-alkoxy-2, 4-dinitro-6-tertiary-butyl-benzenes



Patented July 19, 1949 METHOD FOR THE PREPARATION OF l-ALKOXY-ZA-DINITRO-G-TERTIARY- BUTYL-BENZENES Marion Scott Carpenter, Nutley, andWilliam M.

Easter, Jr., Lodi, dan Corporation,

N. J assignors to The Givaua corporation of New Jersey N Drawing.Application May 24, 1947 Serial No. 750,357:

4 Claims. (Cl. 260-612) This invention relates to novel synthetic muskmaterials and to a process for preparing them. More especially, thepresent invention relates to 1-alkoxy-2,4-dinitro-6-tertiary-butylbenzenes.

The structural formula of our novel musk materials may be represented asfollows:

wherein R is selected from CH3 and C2H5. These dinitro compounds arepale yellow crystalline ma-.

terials having strong musk-like odors. They may be employed in perfumesand cosmetics.

Our novel musk materials are prepared by nitration of compounds havingthe structural formula: l

HaC-

CHO which themselves are prepared by heating a inaterial having thestructural formula:

CH O a R wherein R is a methyl or an ethyl radical, with an oxidationagent such as manganese dioxide in" sulfuric acid, at an elevatedtemperature.

The non-nitrated products as above formed (and which, it will beobserved are aromatic aldehydes) are treated with mixed acids (sulfuricand nitric acids) at temperatures within the range of about 10 and C.

The following examples are given in order more fully to illustrate thisinvention, without however limiting the same to them.

EXAMPLE I Preparation of 3-tertiary-butyZ-4-methoxy toluene 330 litersof iso butylene are passed into an agitated mixture of 1,464 gramsp-cresol methyl ether and 75 grams sulfuric acid 93%, at a temperatureof 22-28 C., as rapidly as the absorption of the gas will permit. About3 hours is required. The oily reaction mixture is washed with dilutecaustic soda solution and until it is neutral and is then distilledinvacuo.

then with water There is first obtained 73 grams of unreacted p; cresolmethyl ether, boiling at 47 C. under 3 mm. of mercury pressure, followedby 2,105 grams of the desiredproduct boiling at 78 C. under 3 mm. ofmercury pressure. This product is a colorless oil having. acongeali-ngpoint of 16 C.

' ExAMPLE 1T u v Preparation of 3Jertiary-butyl-4-methomybenzaldehyde iA mixture of 7 4-methoxy toluene, 221 grams manganese dioxide and 2,000grams 30% sulfuric acid is agitated vigorously for 28 hours at atemperature of 62 C. After cooling to roomtemperature the mix ture isfiltered to remove a small amount of unir e acted manganese dioxide, thepresence of which wouldfimpede the washing of the oilylayer. The

lower layer containing manganese sulfate and sulfuric acid'is discardedand theupper oily layeris washed to neutrality with water and distilled,preferably invacuo.

methoxy toluene. After an intermediate fraction of about 4grams there isthen col ected-at' 117- 122 C. under the same pressureabout 187 grams"-of B-tertiary-butyl 4 methoxy behzaldehyde, which rapidly solidifies toa solid mass; After re-" crystallization from half its weight ofnaphtha,

there is obtained about grams of purified aldehyde. It is a colorlesscrystalline material melting at 549-559 C. and having a somewhatempyreumatic odor. of thefcuir de Russe type.

EXAMPLE III Preparation of I-methoscy-Z 4dim't1'0- fi-tertiary-butylbenzene A solution of 48 grams 3-tertiary-butyl-4-methoxy benzaldehydein 50 grams chloroform is added with stirring and cooling to a mixtureof 41 grams nitric acid 96%, grams sulfuric acid 93% and 200 gramschloroform at a temperature of 0 to 10 C. When the addition is completedthe mixture is quenched by pouring onto crushed ice. The chloroformsolution is separated, Washed with dilute caustic soda solution, thenwith water to neutrality and the chloroform distilled 01f. The residueconsists of 58 grams of yellow oil which congeals to a crystalline massupon cooling. After two crystallizations from alcohol, there is obtainedabout 35 grams of pure l-meth- 400 grams of 8-tertiary-butylg;

There firstpa'sses over at 80 -82 C. under a pressure of 3 mm. ofmercury-- about 226 grams of recovered 3 -tertiary-butyl-4 Preparationof 3-ter tza ry -butyl-4-ethory toluene 42 liters of isobutylene ispassed into an agie tated mixture of 204 grams p-cresol ethyl ether and9 grams sulfuric acid 93%, at a temperature of 22-28 C., as rapidly asthe absorption ofthe gas will permit. About one hour is required. Theoily reaction mixture is washed with dilute caustic soda solution andthen with water until it is neutral and is then distilled in vacuo,There is first obtained 4 grams of unreacted p-cresol ethyl ether,boiling at 57 C. under 3 mm. of mercury pressure, followed by 224 gramsof 3-tertiarybutyl-4-ethoxy toluene boiling at 84 C. under 3 mm. ofmercury pressure. This product is a colorless oil having a mildcharacteristic odor. It has specific gravity (25 C.) .915 and uponslight cooling congeals to a crystalline mass of melting point 7 EXAMPLEV Preparation of 3-tertz'ary-batyl- 4-ethoxy benzaldehyde A mixture of192 grams 3-tertiary-butyl- 4-ethoxy toluene, 100 grams powdered man-'ganese dioxide and 900 grams sulfuric acid 30% is agitated for 28 hoursat a temperature of 6065 C. The mixture is then cooled to roomtemperature, thinned with 200 grams benzene and filtered to remove asmall amount of unreacted manganese dioxide. The lower layer containingmanganese sulphate and sulfuric acid is discarded and the upper layer iswashed with dilute sodium carbonate solution and then with water toneutrality, the solvent distilled ofi andthe remainder distilled invacuo. There is first obtained 104grams of unreacted 3-tertiary-bu-tyl-4-ethoxy toluene, followed by 63 grams of v3-tertiary-butyl-4-ethoxybenzaldehyde boiling at 133 C. under 3% mm. of mercury pressure.- Thealde-- hyde soon ,congeals to a solid mass. After recrystallization fromhalf its weight of naphtha, there is obtained 60 grams of pure aldehydeas colorless needles of melting point 69-70 C. It has an empyreumaticodor quite similar to that of 3-tertiary-butyl-4-methoxy henzaldehyde,but somewhat softer.

EXAMPLE VI I Preparation of 1-ethoary-2,4-dinitro-6-tertiarybutylbenzene Proceedin as in Example III but substituting hyde for the3-tertiary-butyl-4-methoxy-benzaldehyde used in that case, there isobtained about 38 grams of 1-ethoxy-2,4 dinitro 6 tertiarybutyl-benzeneas pale yellow crystals melting at 7979.5 C. and having a strong muskodor.

The foregoing illustrates the practice of this invention which howeveris not to be limited thereby but is to be construed as broadly aspermissible in View of the prior art and limited solely by the appendedclaims. We claim: V 1. The process for preparing compounds having thestructural .iormula:

HaC-C NO:

.. with a, mixture of nitric and sulfuric acids at a temperature withinthe range of about '10 C. to about +20 C.

2. The process of claim 1, wherein the temperature employed is withinthe range'of about 0C. to about 10 C.

3. The process of claim 2, wherein the material treated is3-tertiary-butyl-4-methoxy benzaldehyde. 1

4. The process of claim 2, wherein the material treated is3-tertiary-butyl-4-ethoxy benzaldehyde.

MARION SCOTT CARPENTER. WILLIAM M. EASTER, JR.

REFERENCES CITED UNITED STATES PATENTS Name Date Wirth July 9, 1935OTHER REFERENCES Hanai: Sci. Papers Inst. Phys. Chem. Research, (Tokio)1931, vol. 15; abstract in English in No. 294-296. Abstracted in Chem.Abstracts, vol. 26 (1932), page 1631.

Number Certificate of Correction Patent No. 2,476,815 July 19, 1949MARION SCOTT CARPENTER ET AL. It is hereby certified that error appearsin the printed specification of the above numbered patent requiringcorrection as follows: Column 4, line 21, for C 11 read 0 11 and thatthe said Letters Patent should be read with this correction therein thatthe same may conform to the record of the case in the Patent Office.

Signed and sealed this 20th day of December, A. D. 1949.

THOMAS F. MURPHY,

Assistant Oommissimr of Patents.

